Detergents containing succinic compounds



DETERGENTS CONTAINING SUCCINIC COMPOUNDS Vladimir Dvorkovitz, Kansas City, Mo., and Neil W. Berst and George G. Leist, Evanston, 11]., assignors to The Diversey Corporation, a corporation of Illinois No Drawing. Application July 15, 1955 Serial No. 522,370

4 Claims. (Cl. 252-152) This invention relates to additives that reduce the skin irritation that is normally associated with the use of deter gent formulations, the commercial application of said additives and detergent formulations containing said additives.

We have discovered that when water-soluble polycar boxylic acids such as succinic acid and/or water-soluble salts of said acids, as well as materials that form said salts and/or acids upon hydration or when in contact with the skin, and succinimide are combined with detergents or detergent solutions (i. e., aqueous solution, etc.), they tend to reduce the skin irritation that is normally associated with detergent formulations. The water-soluble salts include alkali metal, amine and ammonium salts; the salts have been found to be generally as effective as the corresponding free acid. These materials shall herein be referred to as additive(s). r

The additives, as well as combinations of the additives, are particularlyeflective when used in conjunction with substantially neutral detergents; however, they may also be employed with alkaline detergents as well as detergent formulations containing mixtures of alkaline detergent(s) plus substantially neutral detergent(s).

The additives may be employed with alkaline detergents such as phosphates, complex phosphates, silicates, soda ash, caustic, borates and the like which may contain alkalimetal, amine and ammoniumsubstituents.

The term substantially neutral detergents includes anionic detergents such as exemplified by Oronite D-60 (about 60% sodium dodecyl benzene sulfonate and about sodium sulfate) as well as nonionic detergents such as exemplified by Triton X100 (isooctylphenyl ether of decaethylene glycol). Anionic detergents such as alkali metal, amine and ammonium salts of alkyl aryl sulfonic acids and nonionic detergents such as alkyl aryl ether alcohols are illustrative of the various substantially hentral detergents that may be employed in combination with one or more of the additives.

One of the conventional methods of studying skin irritation (e. g., in regard to humans) is to intradermally inject 0.5 cc. of the detergent formulation being tested into freshly shaved American chinchilla rabbits. Observations are made after 24 hours and readings are made on the basis of a scale of O (for no irritation) to 5 (for very bad irritation).

Tests were first started using male chinchilla rabbits for test animals in accordance with the above-mentioned conventional test procedure. It wasjfound, however; that about A to about /2 of the test rabbits had large, dark pigmented areasof skin that made the interpretation of results difiicult. Male albino rabbits were then obtained, and a series of conventional tests were made with both types of rabbits to determine if the same results, or at least the same relativeresults would be obtained with either kind of rabbit. The results of these comparison tests are shown in Table I. A series of raw materials common to detergent formulations were injected at concentrations of V2 ounce per gallonwith an injection pattern reading from the back of the rabbit to the front:

where 1-2 were saline solution controls, 3-4, 5-6 and 7-8 were duplicate injections of three raw materials (e. g., 3-4 were tetrasodium pyrophosphate, 5-6 were trisodium phosphate, etc.). Sterile solutions were used for all tests, and observations were made after 24 hours; a rating was given asan average of the two duplicate spots based on the scale of 0 (no irritation) to 5 (extremely bad and spreading irritation).

The data shown in Table I indicates that the degree of irritation was generally only slightly higher with the albino rabbits than with chinchilla rabbits. Thus, male albino rabbits were used in all subsequent tests.

TABLE I Comparison of results obtained with male American chinchilla rabbits and male albino rabbits In subsequent tests, our procedure consisted of injecting 0.5 ml. of solution intradermally into the side of a freshly clipped male albino rabbit. It was found that be carefully clipping the rabbits it was not necessary to shave the small amount of remaining hair. By wetting the area with alcohol, injections and observations were easily made. Tests were usually made at concentrations of A, /2 and 1 ounce per gallon; these concentrations gave a degree of irritation that was definite, but not excessive. Eight injections were made to one rabbit side, and a replicate test was made in most cases on another rabbit. Observations were made after 24 hours and ratings were given on the basis of a scale wherein 0 represents no irritation andfS represents very bad or mailirnurn irritation. The effect ofan additive on the deter gents was bestdetected when the detergent alone (without the additive) had a rating of 2 to 3. r

The tests tabulated in Tables II-VI were made on albino rabbits. Additives of various concentrations were tions were /1 ounce pergallon, V2 ounce per gallon and 5 TABLE v Summary of the efieet of cetyl alcohol-urea complex on reducing: skin irritation. caused by various detergent components 1 Component Causing Irritation Degree of Concentration of Irritation Cetyl Alcohol- Treated- Urea Complex, Cone, Untreated Percent of Solids Name 02./ Gal. 24 Hrs. After 1 l 1 Injection 1.24 Sodium Metasilicate- 1 4 -4 2. do 1 4 4.76 1 4 0.5 2 --3 0.5 2. 53 0.5 3 -3 1 0.25 0. 50.& 2. 0. 25 0.5-0.5 4. 0.25 0.5-0.5 1. 1 1 -3 2. 1 2 -3 1 2. 5-3 1. 0.5 0.5-1.5 2. 0.5 1 -l.5 4. 0.5 1 --1.5 1. 0. 25 -O.5 2. 0. 25 0 -0.5 4. 0. 25 0 0.5 2. 1 l -2 4. 1 1 -2 9. 1 1 -2 2. 0.5 0.5-1 4. 0.5 0.5-1 9. 0.5 0. -1 2. 0. 25 0.5-0.5 4. 0. 25 0.5-0.5 9. 0. 25 0. 5-0. 5

Table VI shows the effect of various additives upon various compositions that contain more than 1 detergent product.

TABLE VI Efiect of additives on reducing skin irritation caused by various detergent formulations FORMULATION XF-lOO 1 Reaction at 1 Oz./ Gal. of Formulated Product Cone. of Additive, Additive Percent of Replicate 1 Replicate 2 Total Solids Wlth- With With- With out out FORMULATION XF-20O 1 ii Aid 9.1 2 0.5 2 0.5 i

TIDE

TABLE VI-Contmued SURF 4 succinic Acid 9. 1 3 2 3 1. 5 D0 4. 76 3 2 3 1. 5 Do 2. 44 3 1 3 1. 5

Cetyl Alcohol-Urea. .Oom-

plex 9.1 3 0.5 2 0.5 4. 76 3 1 2 l 2. 44 3 0. 5 2 1. 5

1 Percent by weight 1 Soda ash 54. 77 Sodium tripolyphosphate 28.00 Alkyl aryl sulfonate; 15.00 Oetyl phenol polyoxyethylene ether 2.00 Sodium carboxymethylcellulose-.. 0.23 2 Sodium tripolyphosphate 22.00 Sodium metasilicate 16. 00 Sodium carboxymethylcellulose 0. 23 Soda as 58. 27 Sodium dodecyl benzene sulionate 80 Ethylene glycol 0. 70

11 1 Ogntains sodium lauryl sulfate, sodium tripolyphosphate and sodi s ce e.

4 Contains sodium dodecyl benzene sulionate, sodium tripolyphosphate and sodium silicate.

The additives have been shown to be effective when employed with the detergent in quantities as low as about 0.1 by weight (based upon the weight of the total solids in the detergent plus additive compositions), as shown in Tables 11 and III, but we do not limit the invention to this concentration, although in order to insure the most effective results we prefer not to use less than this amount. If desired, higher concentrations of the additive may be employed. The term succinic acid derivatives shall hereinafter refer to water-soluble succinic acid salts (i. e., amine salts, alkali metal salts, ammonium salts) and/or materials that form succinic acid and/or water-soluble salts of succinic acid upon hydration or when in contact with the skin.

Although the present invention has been described in conjunction with preferred embodiments, it is to be understood that modifications and variations may be resorted to without departing from the spirit and scope of the invention as those skilled in the art will readily understand. Such variations and modifications are considered to be within the purview and scope of the invention and appended claims.

We claim:

I. A non-acid detergent composition having a reduced tendency to irritate the skin and consisting essentially of (1) a synthetic organic detergent selected from the group consisting of sodium higher alkylbenzene sulfonates and higher alkylphenyl ethers of polyethylene glycol, and (2) at least 0.1% by weight, based on total solids, of a Watersoluble, skin-irritation reducing additive selected from the group consisting of succinic acid, water-soluble alkali metal salts thereof, and succinimide, said synthetic organic detergent being present in said composition in an amount in excess of said additive.

2. A non-acid detergent composition having a reduced tendency to irritate the skin and consisting essentially of (l) a mixture of (A) a synthetic organic detergent selected from the group consisting of sodium higher alkylbenzene sulfonates and higher alkylphenyl ethers of polyethylene glycol plus (B) an alkaline inorganic detergent which serves as a detergent builder, and (2) at least 0.1% by weight, based on total solids, of a water-soluble, skinirritation reducing additive selected from the group consisting of succinic acid, water-soluble alkali metal salts thereof, and succinimide, said mixture being present in said composition in an amount in excess of said additive.

3. A non-acid detergent composition having a reduced tendency to irritate the skin and consisting essentially of (l) a mixture of (A) a synthetic organic detergent selected from the group consisting of sodium higher alkylbenzene sulfonates and higher alkylphenyl ethers of polyethylene glycol plus (B) an alkaline inorganic detergent which serves as a detergent builder, and (2) at least 0.1% by Weight, based on total solids, of a Water-soluble, skin-irritation reducing additive selected from the group consisting of succinic acid, water-soluble alkali metal salts thereof, and succinirnide, said synthetic organic detergent being present in said composition in an amount (a) in excess of said additive and (b) in excess of said detergent builder.

4. A non-acid detergent composition having a reduced tendency to irritate the skin and consisting essentially of (1) a mixture of (A) a synthetic organic detergent selected from the group consisting of sodium higheralkylbenzene sulfonates and higher alkylphenyl ethers of polyethylene glycol plus (B) an alkaline inorganic detergent which serves as a detergent builder, and (2) at least 0.1%

by Weight, based on total solids, of a Water-soluble, skinirritation reducing additive selected from the group consisting of succinic acid, water-soluble alkali metal salts thereof, and succinimide, said inorganic detergent builder being present in said composition in an amount (a) in excess of said additive and (b) in excess of said synthetic organic detergent.

References Cited in the file of this patent UNITED STATES PATENTS 2,562,156 Vitalis July 24, 1951 2,584,017 Dvorkovitz et al Jan. 29, 1952 2,628,199 Lowenheim Feb. 10, 1953 2,675,356 Woodworth et a1 Apr. '13, 1954 2,711,397 Owen June 21, 1955 2,717,878 Malkemus Sept. 13, 1955 FOREIGN PATENTS 474,032 Great Britain Oct. 25, 1937 Chemical Formulary, Bennett, vol. 9, page 121, Chemical Pub. Co., Inc., N. Y. (1951). 

4. A NON-ACID DETERGENT COMPOSITION HAVING A REDUCED TENDENCY TO IRRITATE THE SKIN AND CONSISTING ESSENTIALLY OF (1) A MIXTURE OF (A) A SYNTHETIC ORGANIC DETERGENT SELECTED FROM THE GROUP CONSISTING OF SODIUM HIGHER ALKYLBEZENE SULFONATES AND HIGHER ALKYLPHENYL ETHERS OF POLYETHYLENE GLYCOL PLUS (B) AN ALKALINE INORGANIC DETERGENT WHICH SERVES AS A DETERGENT BUILDER, AND (2) AT LEAST 0.1% BY WEIGHT, BASED ON TOTAL SOLIDS, OF WATER-SOLUBLE, SKINIRRITATION REDUCING ADDITIVE SELECTED FROM THE GROUP CONSISTING OF SUCCINIC ACID, WATER-SOLUBLE ALKALI METAL SALTS THEREOF, AND SUCCINIMIDE, SAID INORGANIC DETERGENT BUILDER BEING PRESENT IN SAID COMPOSITION IN AN AMOUNT (A) IN EXCESS OF SAID ADDITIVE AND (B) IN EXCESS OF SAID SYNTHETIC ORGANIC DETERGENT. 